JPS63270397A - Highly oriented lithium niobate thin film and production thereof - Google Patents
Highly oriented lithium niobate thin film and production thereofInfo
- Publication number
- JPS63270397A JPS63270397A JP10242287A JP10242287A JPS63270397A JP S63270397 A JPS63270397 A JP S63270397A JP 10242287 A JP10242287 A JP 10242287A JP 10242287 A JP10242287 A JP 10242287A JP S63270397 A JPS63270397 A JP S63270397A
- Authority
- JP
- Japan
- Prior art keywords
- lithium niobate
- thin film
- precursor
- substrate
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000010409 thin film Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000010304 firing Methods 0.000 claims abstract description 5
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 4
- 239000010980 sapphire Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 6
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims 2
- 239000002356 single layer Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 17
- 239000010408 film Substances 0.000 abstract description 17
- 229910003327 LiNbO3 Inorganic materials 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 7
- 239000010955 niobium Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- -1 Lithium alkoxide Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1225—Deposition of multilayers of inorganic material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高純度で組成が化学量論比に制御された低温で
焼成できる、特に厚さが数１００人ないし数μｍの配向
したニオブ酸リチウム薄膜およびその製造方法に関する
ものである。Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to the production of oriented niobic acid having a high purity and a composition controlled to a stoichiometric ratio, which can be fired at a low temperature, and in particular has a thickness of several hundred to several μm. This invention relates to a lithium thin film and its manufacturing method.
（従来の技術）
ニオブ酸リチウムは圧電性、焦電性をもつためその単結
晶はＳＡＷデバイス、赤外線センサーとして応用されて
いる。ニオブ酸リチウムは化学量論組成付近に固溶領域
をもち、調和溶融液組成は化学量論組成と異なるため、
組成を制御した化学量論組成の均質なニオブ酸リチウム
単結晶の育成は困難であった。また、単結晶製造の際に
は、１０００℃以上の高温が必要であるためその製造装
置は大型なものとなっていた。そのためニオブ酸リチウ
ムのち密で、不純物を含まない結晶性の高い焼結体の薄
膜を作成し、焼結の際に分極する等の方法によって単結
晶の代わりにＳＡＷデバイスや赤外線センサーとして用
いる試みがなされてきた。(Prior Art) Lithium niobate has piezoelectric and pyroelectric properties, so its single crystals are used as SAW devices and infrared sensors. Lithium niobate has a solid solution region near the stoichiometric composition, and the harmonic melt composition differs from the stoichiometric composition.
It has been difficult to grow a homogeneous lithium niobate single crystal with a controlled stoichiometric composition. Furthermore, since single crystal production requires high temperatures of 1000° C. or higher, the production equipment has been large. Therefore, attempts have been made to create a thin film of lithium niobate that is dense, highly crystalline sintered material that does not contain any impurities, and to use it as a SAW device or infrared sensor instead of a single crystal by polarizing it during sintering. It has been done.
その方法の一つとして、粉粒体状のニオブ酸リチウムを
均一に分散させた溶液を基板上に塗布し焼結する方法が
あるが、ち密でクラックやピンホールのない膜を作成す
ることは困難であり、焦電体、圧電体として望ましい厚
さ数μｍ以下の薄膜を製造することは、極めて困難であ
った。焼結を行うには１０００℃以上の高温が必要なた
め基板の材料も限られ、製造装置も大型なものとなって
しまっていた。この他、ニオブ酸リチウム膜の製造方法
として、スパッタリング法、真空蒸着法、気相反応法等
が検討されているが、これらの方法においてはち密なも
のは得がたく、化学量論比の制御が極めて困難であるこ
とにより優れたニオブ酸リチウム薄膜は得られていない
。One method is to apply a uniformly dispersed solution of powdered lithium niobate onto the substrate and sinter it, but it is difficult to create a dense film without cracks or pinholes. It has been extremely difficult to manufacture thin films with a thickness of several μm or less, which are desirable as pyroelectric and piezoelectric materials. Sintering requires a high temperature of 1,000°C or higher, which limits the materials available for the substrate and requires large manufacturing equipment. Other methods of producing lithium niobate films, such as sputtering, vacuum evaporation, and gas-phase reaction methods, are being considered, but these methods cannot produce dense films, and it is difficult to control the stoichiometric ratio. However, it is extremely difficult to obtain an excellent lithium niobate thin film.
ニオブ酸リチウム薄膜の製造方法は学会などで公表され
ている例はあるが、配向させたニオブ酸リチウム薄膜を
得る方法についてはまだ提案されていない。Although methods for producing lithium niobate thin films have been published at academic conferences, no method for obtaining oriented lithium niobate thin films has yet been proposed.
（発明が解決しようとする問題点〉
従来の粉末塗布の後焼結する方法、スパッタリング法で
はいずれの方法においてもち密で不純物や第二相がなく
化学量論比に組成を制御された結晶性の高いニオブ酸リ
チウム膜を製造することは不可能であった。また、焦電
体、圧電体として必要な数１００λ以上の膜厚を得るた
めには、スパッタリング法では膜の成長速度が遅くスパ
ッタリングの時間がかかり過ぎ、逆に粉末塗布の後焼結
する方法では圧電体、焦電体として望ましい数μｍ以下
の膜厚を得ることは困難であった。(Problems to be solved by the invention) Both the conventional method of applying powder and then sintering, and the sputtering method produce crystallinity that is dense, free of impurities and secondary phases, and whose composition is controlled to a stoichiometric ratio. It has been impossible to manufacture a lithium niobate film with a high film thickness.In addition, in order to obtain a film thickness of several hundred λ or more, which is necessary for pyroelectric and piezoelectric materials, sputtering has a slow film growth rate, and sputtering is necessary. On the other hand, it was difficult to obtain a film thickness of several micrometers or less, which is desirable for piezoelectric materials and pyroelectric materials, by the method of applying powder and then sintering it.
また、ニオブ酸リチウム膜の製造には１０００℃以上の
高温を発生することのできる電気炉が必要であり、また
基板の材質も限られたものしか使用できないといった問
題点があった。In addition, manufacturing a lithium niobate film requires an electric furnace capable of generating a high temperature of 1000° C. or higher, and there are also problems in that only limited materials can be used for the substrate.
さらに、いずれの方法によっても配向した結晶性の薄膜
を得ることは不可能であった。Furthermore, it was impossible to obtain an oriented crystalline thin film by any of the methods.
本発明の目的は、配向させる問題、膜のち密さの問題、
純度の問題、組成を制御する問題、膜厚の問題、熱処理
に高温が必要とされるといっな問題点を解決したニオブ
酸リチウム薄膜とその製造方法を提供することにある。The purpose of the present invention is to solve the problem of orientation, film density,
The object of the present invention is to provide a lithium niobate thin film that solves problems such as purity, composition control, film thickness, and the need for high temperatures for heat treatment, and a method for producing the same.
（問題点を解決するための手段）
本発明は配向された組成式がＬｉＮｂ０９であるところ
のち密で結晶性の高いニオブ酸リチウム薄膜およびその
製造方法である０本発明においてその製造方法はエトキ
シリチウムとペンタエトキシニオブのモル比が１＝１と
なるように混合、溶解し、還流を行い、複合アルコキシ
ドを作成し、この複合アルコキシドを部分加水分解し、
ＬｉＮｂＯ３の前駆体を作成し、得られたＬｉＮｂＯ３
の前駆体を濃縮し、該前駆体溶液をサファイア単結晶基
板上に塗布して４００℃以上の温度で加熱焼成する工程
を少なくとも１回以上繰り返し、当該基板上にニオブ酸
リチウム薄膜を多層に積層せしめることを特徴とするニ
オブ酸リチウム薄膜の製造方法である。(Means for Solving the Problems) The present invention provides a dense and highly crystalline lithium niobate thin film having an oriented compositional formula of LiNb09, and a method for producing the same. and pentaethoxyniobium are mixed and dissolved so that the molar ratio is 1=1, reflux is performed to create a composite alkoxide, and this composite alkoxide is partially hydrolyzed,
Create a LiNbO3 precursor and obtain the LiNbO3
The process of concentrating the precursor, applying the precursor solution onto a sapphire single crystal substrate, and heating and firing it at a temperature of 400°C or higher is repeated at least once, and a multilayer lithium niobate thin film is laminated on the substrate. This is a method for producing a lithium niobate thin film, characterized by:
さらに詳しく述べると次のとおりである。出発原料とし
てリチウムのアルコキシドとニオブのアルコキシドを用
いこれらのモル比が１：１となるように脱水、精製した
アルコールに混合、溶解した。アルコールは常温で液体
であれば良く、好ましくはエタノールを用いる。この溶
液を２２時間以上攪はん、還流しながら反応させること
によって複合アルコキシドを生成させる。これらの操作
は金属アルコキシドが空気中の水分で容易に加水分解す
るため、乾燥した窒素雰囲気中で行った。このように調
製された溶液に複合金属アルコキシドが加水分解するの
に必要なモル数以上の水を脱炭酸水の形で、好ましくは
溶媒のアルコールにて希釈した形で滴下する。この後、
攪はん、還流を続は反応を完結させ、ＬｉＮｂＯ３の前
駆体が得られる。More details are as follows. Lithium alkoxide and niobium alkoxide were used as starting materials and mixed and dissolved in dehydrated and purified alcohol so that the molar ratio thereof was 1:1. The alcohol only needs to be liquid at room temperature, and ethanol is preferably used. A composite alkoxide is produced by reacting this solution while stirring and refluxing the solution for 22 hours or more. These operations were performed in a dry nitrogen atmosphere because metal alkoxides are easily hydrolyzed by moisture in the air. Water in an amount equal to or greater than the number of moles required for hydrolysis of the composite metal alkoxide is added dropwise to the solution thus prepared in the form of decarbonated water, preferably diluted with alcohol as a solvent. After this,
After stirring and refluxing, the reaction is completed and a LiNbO3 precursor is obtained.
得られたＬｉＮｂＯ３の前駆体を濃縮しこの溶液に単結
晶基板を浸漬し、一定速度で引き上げることにより基板
表面にコーテイング膜を形成した。数分間乾燥させた後
、酸素と水蒸気の混合気流中で、ついで乾燥酸素気８流
中で加熱処理することによって配向したニオブ酸リチウ
ム単相の薄膜を得ることができる。この後、浸漬、引き
上げ、乾燥、加熱処理の工程を数回繰り返すことにより
、所望の厚さの配向したニオブ酸リチウム薄膜を得るこ
とができる。The obtained LiNbO3 precursor was concentrated and a single crystal substrate was immersed in this solution and pulled up at a constant speed to form a coating film on the substrate surface. After drying for several minutes, a heat treatment is performed in a mixed flow of oxygen and water vapor, and then in 8 flows of dry oxygen to obtain an oriented single-phase lithium niobate thin film. Thereafter, by repeating the steps of dipping, pulling up, drying, and heat treatment several times, an oriented lithium niobate thin film with a desired thickness can be obtained.
（作用）
本発明で出発原料として用いているリチウムとニオブの
アルコキシドは蒸留等の方法によって精製することが可
能なため高純度なセラミックス薄膜の原料を提供するこ
とができる。また、不純物を含まないため正確に金属元
素のモル数が等しくなるように秤量することができる。(Function) Since the lithium and niobium alkoxides used as starting materials in the present invention can be purified by methods such as distillation, they can provide raw materials for highly pure ceramic thin films. Furthermore, since it does not contain impurities, it can be weighed accurately so that the number of moles of metal elements is equal.
このため、最終的な生成物であるニオブ酸リチウムのニ
オブとリチウムのモル比を正確に１＝１に制御すること
ができる。Therefore, the molar ratio of niobium to lithium in the final product, lithium niobate, can be precisely controlled to 1=1.
さらに、本発明によれば最終的にニオブ酸リチウムを得
るのに必要な熱処理の温度を従来の方法のような１ｏｎ
ｅ℃以上の高温から１０００℃未満、さらには３００℃
程度の低温にすることが出来るため、簡便な加熱装置と
ガラス等の容器中でニオブ酸リチウム薄膜を製造するこ
とができる。さらには、本発明によって得られるニオブ
酸リチウム薄膜はその組成を均一にすることができるた
め、不純物としての第二相の生成を抑制できるだけでな
く、原料溶液中でニオブとリチウムの各原子が均一に混
合しているため結晶化しやすく結晶化度の高いニオブ酸
リチウム薄膜が得られる。また、配向されているため、
現在応用面で興味のある焦電性、圧電性が単結晶に近い
優れたものとなる。Furthermore, according to the present invention, the temperature of the heat treatment necessary to finally obtain lithium niobate can be reduced to 1 on, unlike the conventional method.
High temperatures from e℃ and above to less than 1000℃ and even 300℃
Since the temperature can be kept at a low temperature of about 100 mL, a lithium niobate thin film can be produced in a simple heating device and a container made of glass or the like. Furthermore, since the lithium niobate thin film obtained by the present invention can have a uniform composition, not only can the formation of a second phase as an impurity be suppressed, but also the niobium and lithium atoms are uniformly distributed in the raw material solution. Because it is mixed with lithium niobate, it is easy to crystallize and a lithium niobate thin film with a high degree of crystallinity can be obtained. Also, because it is oriented,
The pyroelectricity and piezoelectricity, which are currently of interest in terms of applications, are excellent and are close to those of single crystals.
（実施例）
以下、本発明を実施例によりさらに詳細に説明する。た
だし、本発明の範囲は下記実施例により何等限定される
ものではない。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the scope of the present invention is not limited in any way by the following examples.
ニオブ及びリチウムの複合アルコキシド溶液の調製：エ
トキシリチウム： ＬｉＯＣ２Ｈ５とペンタエトキシニ
オブ： Ｎｂ＜０Ｃ２）１５）ｓとをＬｉ ： Ｎｂの
比が１＝１となる如くそれぞれ秤取し、脱水、精製した
エタノール中に混合、溶解した。この溶液を２４時間攪
はん、還流した。これらの操作は、エトキシリチウムと
ペンタエトキシニオブが空気中の水分により容易に加水
分解されるため、乾燥した窒素雰囲気中で行った。得ら
れた生成物は、１）Ｉ−Ｎ１４Ｒ及びＩＲのスペクトル
変化から複合アルコキシドであることが分かった。Preparation of composite alkoxide solution of niobium and lithium: Ethoxylithium: LiOC2H5 and pentaethoxyniobium: Nb<0C2)15)s were weighed out so that the Li:Nb ratio was 1=1, and dehydrated and purified ethanol. mixed and dissolved in it. This solution was stirred and refluxed for 24 hours. These operations were performed in a dry nitrogen atmosphere because ethoxylithium and pentaethoxyniobium are easily hydrolyzed by moisture in the air. The obtained product was found to be a complex alkoxide from 1) changes in I-N14R and IR spectra.
還流の時間により複合アルコキシドの溶液中での配位状
態が変化していた。この溶液中の複合アルコキシドの配
位状態がその後のニオブ酸リチウム作成のための熱処理
の容易さを決定する。The coordination state of the complex alkoxide in the solution changed depending on the reflux time. The coordination state of the complex alkoxide in this solution determines the ease of subsequent heat treatment for producing lithium niobate.
ニオブ酸リチウム前駆体の調製：
得られた複合アルコキシドにエタノールに希釈した脱炭
酸水を滴下して加水分解を行った。さらに、攪はん、還
流を２４時間続は反応を完結させた。この後、エタノー
ルを蒸発させ、ニオブ酸リチウムの前駆体濃度が０．２
ｍｏＬ／ｆと０．６ｒｎｏｊ！、／４である２種類の溶
液を作成した。Preparation of lithium niobate precursor: Decarbonated water diluted with ethanol was added dropwise to the obtained composite alkoxide to perform hydrolysis. Further, stirring and refluxing were continued for 24 hours to complete the reaction. After this, the ethanol was evaporated and the concentration of the lithium niobate precursor was 0.2.
moL/f and 0.6rnoj! , /4 were prepared.
ニオブ酸リチウム前駆体の基板への塗布および加熱処理
二
得られたニオブ酸リチウムの前駆体濃度が０．２ｒｎｏ
ＪＬ／Ａの濃縮溶液にａ −Ａ Ｑ ２０３（０００１
）基板を浸漬し一定の速度で引き上げ塗布を行い、乾燥
させた。この後得られたニオブ酸リチウムの前駆体のコ
ーテイング膜を２５０℃で酸素と水蒸気の混合雰囲気中
にて１時間半、ついで乾燥酸素中で１時間保持し加熱処
理した。この後、ニオブ酸リチウムの前駆体濃度が０．
６ｒｎｏｉ／ｆの濃縮溶液に浸漬し一定の速度で引き上
げ塗布を行い、乾燥させた。ついで、３５０℃、４００
℃、５００℃の３種類の温度条件下で酸素と水蒸気の混
合雰囲気中にて１時間半、ついで乾燥酸素中で１時間保
持し加熱処理した。この浸漬、引き上げ、乾燥、加熱処
理（３５０℃、４００℃、５００℃）の工程を繰り返し
て、ち密なＣ軸配向した結晶性のＬｉＮｂＯ５薄膜を合
成することができた。これら得られた薄膜を粉末Ｘ線回
折法により調べた結果、３５０℃加熱処理では結晶化は
見られなかったものの、４００℃加熱処理で（００６）
配向結晶化が見られ、５００℃加熱処理ではほぼ完全に
近い配向膜となっていることが確認された。 ′
第１図は実施例にて加熱処理温度を変えて最終的に得ら
れた薄膜のＸ線回折図を示したものである。第１図の図
中において○印をつけたものはＬｉＮｂＯ５薄膜の（０
０６）回折線のピークを、Δ印をつけたものは基板のα
−＾Ｑ ２０３（００６）回折線のピークをそれぞれ示
すものである。Application of lithium niobate precursor to substrate and heat treatment 2. Precursor concentration of lithium niobate obtained is 0.2rno
a-A Q 203 (0001
) The substrate was dipped, pulled up at a constant speed, applied, and dried. The coating film of the lithium niobate precursor thus obtained was heated at 250° C. by being held in a mixed atmosphere of oxygen and water vapor for 1.5 hours and then in dry oxygen for 1 hour. After this, the concentration of the lithium niobate precursor was reduced to 0.
It was immersed in a concentrated solution of 6 rnoi/f, pulled up at a constant speed, applied, and dried. Then, 350℃, 400℃
The sample was heat-treated under three temperature conditions of 500°C and 1.5 hours in a mixed atmosphere of oxygen and water vapor, and then held in dry oxygen for 1 hour. By repeating this process of dipping, pulling, drying, and heat treatment (350°C, 400°C, 500°C), a dense C-axis oriented crystalline LiNbO5 thin film could be synthesized. As a result of examining these obtained thin films by powder X-ray diffraction, it was found that no crystallization was observed in the heat treatment at 350°C, but (006) was observed in the heat treatment at 400°C.
Oriented crystallization was observed, and it was confirmed that the 500° C. heat treatment resulted in a nearly perfectly oriented film. ' Figure 1 shows the X-ray diffraction patterns of the thin films finally obtained by changing the heat treatment temperature in Examples. In the diagram of Fig. 1, the parts marked with a circle are (0) of the LiNbO5 thin film.
06) The peak of the diffraction line marked with Δ is the α of the substrate.
-^Q The peaks of the 203 (006) diffraction line are shown.
（発明の効果）
このように、本方法によれば配向した結晶性の高いニオ
ブ酸リチウム薄膜を従来の方法に比べて極めて低温にて
製造することができる。(Effects of the Invention) As described above, according to the present method, an oriented lithium niobate thin film with high crystallinity can be produced at a much lower temperature than conventional methods.
この発明はこのようにち密な配向した結晶性のニオブ酸
リチウム薄膜の低温焼成を可能にしたものでありニオブ
酸リチウムを用いた圧電素子、焦電素子等の種々の応用
にその活用が期待されるものである。This invention enables low-temperature firing of a tightly oriented crystalline lithium niobate thin film, and is expected to be used in various applications such as piezoelectric elements and pyroelectric elements using lithium niobate. It is something that
第１図は実施例において最終的に得られたＬｉＮｂＯ３
薄膜のＸ線回折図である。
第１ 口
○
４００’Ｃ
○
ＣｕＫａ２θFigure 1 shows the LiNbO3 finally obtained in the example.
It is an X-ray diffraction diagram of a thin film. 1st mouth ○ 400'C ○ CuKa2θ
Claims (1)
オブ酸リチウムをサファイア単結晶基板上に単層または
多層に積層せしめてなることを特徴とする高配向ニオブ
酸リチウム薄膜。 ２、エトキシリチウムとペンタエトキシニオブのモル比
が１：１となるように混合、溶解し、還流を行い、複合
アルコキシドを作成し、この複合アルコキシドを部分加
水分解し、ＬｉＮｂＯ＿３の前駆体を作成し、得られた
ＬｉＮｂＯ＿３の前駆体を濃縮し、該前駆体溶液をサフ
ァイア単結晶基板上に塗布して４００℃以上の温度で加
熱焼成する工程を少なくとも１回以上繰り返し、当該基
板上にニオブ酸リチウム薄膜を多層に積層せしめること
を特徴とする高配向ニオブ酸リチウム薄膜の製造方法。[Claims] 1. A highly oriented lithium niobate thin film, characterized in that it is formed by laminating oriented lithium niobate having the composition formula LiNbO_3 in a single layer or in multiple layers on a sapphire single crystal substrate. 2. Mix and dissolve ethoxylithium and pentaethoxyniobium in a molar ratio of 1:1, reflux to create a composite alkoxide, and partially hydrolyze this composite alkoxide to create a precursor of LiNbO_3. The process of concentrating the obtained LiNbO_3 precursor, applying the precursor solution onto a sapphire single crystal substrate, and heating and firing it at a temperature of 400°C or higher is repeated at least once, and lithium niobate is deposited on the substrate. A method for producing a highly oriented lithium niobate thin film, which comprises laminating multiple thin films.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10242287A JPS63270397A (en) | 1987-04-24 | 1987-04-24 | Highly oriented lithium niobate thin film and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10242287A JPS63270397A (en) | 1987-04-24 | 1987-04-24 | Highly oriented lithium niobate thin film and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63270397A true JPS63270397A (en) | 1988-11-08 |
| JPH0375518B2 JPH0375518B2 (en) | 1991-12-02 |
Family
ID=14327014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10242287A Granted JPS63270397A (en) | 1987-04-24 | 1987-04-24 | Highly oriented lithium niobate thin film and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63270397A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5051280A (en) * | 1990-10-01 | 1991-09-24 | Eastman Kodak Company | Low temperature synthesis of alkali metal niobates and tantalates |
| JPH08212830A (en) * | 1994-11-11 | 1996-08-20 | Fuji Xerox Co Ltd | Orienting ferroelectric thin film element and its manufacture |
-
1987
- 1987-04-24 JP JP10242287A patent/JPS63270397A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5051280A (en) * | 1990-10-01 | 1991-09-24 | Eastman Kodak Company | Low temperature synthesis of alkali metal niobates and tantalates |
| JPH08212830A (en) * | 1994-11-11 | 1996-08-20 | Fuji Xerox Co Ltd | Orienting ferroelectric thin film element and its manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0375518B2 (en) | 1991-12-02 |
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